Catalysts for gas phase polymerization and process

Abstract

The present disclosure provides a catalyst system. In an embodiment, the catalyst system includes a precatalyst comprising a phenoxy imine precatalyst. The precatalyst has a structure of Formula 1: wherein R 1 each is independently a C 5 to C 20 alkyl group, and X each is independently a halogen atom.

Description

CATALYSTS FOR GAS PHASE POLYMERIZATION AND PROCESSBACKGROUND

[0001] Gas-phase single reactor technologies provide for the synthesis of olefin polymers (and ethylene / a-olefin copolymers in particular) polymerized with a high molecular weight component and a low molecular weight component (also known as a bimodal copolymer). However, utilization of a single polymerization reactor limits the comonomer distribution across the high molecular weight component ("HMW") and the low molecular weight component ("LMW") of the bimodal copolymer. Polymers with proportionally more comonomer content in the HMW component are known to exhibit an improved balance of various product properties, such as improved balance of slow crack growth resistance (SCGR) and long-term hydrostatic test performance (for pipes); improved balance of environmental stress cracking resistance (ESCR) and swell properties for (blow molded articles); and improved balance of ESCR and processability for wire and cable applications.

[0002] The art recognizes the need for a catalyst system for use in a single polymerization reactor configuration capable of producing ethylene-based polymer, and ethylene copolymer in particular, with increased comonomer content in the HMW component for improved product performance. The art further recognizes the need for a catalyst with greater stability as a solution in a hydrocarbon solvent.SUMMARY

[0003] The present disclosure provides a catalyst system. In an embodiment, the catalyst system includes a precatalyst comprising a phenoxy imine precatalyst. The precatalyst has a structure of Formula 1:(Formula 1) whereinR1each is independently a C5 to C20 alkyl group, and X each is independently a halogen atom.

[0004] The present disclosure provides a process. In an embodiment, the process includes polymerizing ethylene with one or more a-olefins, under polymerization conditions, with a catalyst system. The catalyst system includes a phenoxy imine precatalyst having a structure of Formula 1(Formula 1) whereinR1each is independently a C5 to C20 alkyl group, andX each is independently a halogen. The catalyst system also includes an activator. The process includes forming an ethylene / a-olefin polymer.BRIEF DESCRIPTION OF THE DRAWINGS

[0005] FIG. 1 is a schematic representation of the chemical reaction pathway for the synthesis of a precatalyst of Formula (2) in accordance with an embodiment of the present disclosure.

[0006] FIG. 2 is a schematic representation of the chemical reaction pathway for the synthesis of a precatalyst of Formula (3) in accordance with an embodiment of the present disclosure.

[0007] FIG. 3A(i) is the precatalyst of Formula (5) with distinct hydrogens labeled A-L.

[0008] FIG 3A(ii) shows2H NMR spectrums with peak labels corresponding to the hydrogen labels in FIG 3A(i) for the precatalyst of Formula (5) aged in hexane solvent at day 1 (Experiment 1 "Exp 1"), 2 weeks (Exp 2), and 4 weeks (Exp 3).

[0009] FIG. 3 B(i) is the precatalyst of Formula (2) with distinct hydrogens labeled A-Q.

[0010] FIG. 3 B(ii) shows1H NMR spectrums with peak labels corresponding to the hydrogen labels in FIG. 3 B(i) for the precatalyst of Formula (2) aged in hexane solvent at day 1 (Exp 1), day 12 (Exp 2), 10 weeks (Exp 3, 4) and 13 months (Exp 5)).

[0011] FIG. 3C(i) is the precatalyst of Formula (3) with distinct hydrogens labeled A-K.

[0012] FIG. 3C(ii) shows1H NMR spectrums with peak labels corresponding to the hydrogen labels in FIG. 3C(i) for the precatalyst of Formula (3) aged in hexane solvent at day 1 (Exp 1), 2 weeks (Exp 2), 4 weeks (Exp 3), and 14 months (Exp 4).

[0013] FIG. 4 shows the GPC traces for CS3, IE20, I E21, and IE22.

[0014] FIG. 5 shows the GPC traces for CS4, IE23, IE24, and IE25.DEFINITIONS

[0015] Any reference to the Periodic Table of Elements is that as published by CRC Press, Inc., 1990-1991. Reference to a group of elements in this table is by the new notation for numbering groups.

[0016] For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent US version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0017] The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (e.g., 1 or 2; or 3 to 5; or 6; or 7), any subrange between any two explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0018] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date of this disclosure.

[0019] The term "activator" refers to a compound that chemically reacts with a precatalyst in a manner that converts the precatalyst into a catalytically active catalyst. A nonlimiting example of an activator is methylaluminoxane.

[0020] A "catalyst" is a material that enhances rate of a reaction (e.g., the polymerization of ethylene and a-olefin, for example) and is not completely consumed thereby.

[0021] A "catalyst system" is a combination of one or more precatalyst per se and an activator, such as a methylaluminoxane, a support material on which the catalyst is disposed, a carrier material in which the catalyst is disposed, or a combination of any two or more thereof, or a reaction product of a reaction thereof.

[0022] The term "composition" refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0023] The terms "comprising," "including," "having" and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed. The term "or" unless stated otherwise, refers to the listed members individually as well as in any combination.

[0024] An "ethylene-based polymer" or "ethylene polymer" is a polymer that contains a majority amount, or greater than 50 mol%, of polymerized ethylene based on the weight of the polymer, and, optionally, may comprise at least one comonomer.

[0025] An "ethylene / a-olefin interpolymer" is an ethylene-based polymer that contains a majority amount of polymerized ethylene, based on the mole percent of the interpolymer, and at least one a-olefin.

[0026] A "feed" is a quantity of reactant or reagent that is added or "fed" into a reactor. In continuous polymerization operation, each feed independently may be continuous or intermittent. The quantities or "feeds" may be measured, e.g., by metering, to control amounts and relative amounts of the various reactants and reagents in the reactor at any given time.

[0027] A "feed line" is a pipe or conduit structure for transporting a feed.

[0028] A "hydrocarbon " is a compound that contains only hydrogen and carbon atoms. The hydrocarbon can be (i) branched or unbranched, (ii) saturated or unsaturated (iii) cyclic or acyclic, and (iv) any combination if (i)-(iii). Nonlimiting examples of hydrocarbons include alkanes, alkenes, and alkynes.

[0029] An "olefin-based polymer" or "polyolefin" is a polymer that contains a majority amount, or greater than 50 mol%, of polymerized olefin monomer, for example, ethylene or propylene, (based on the weight of the polymer), and optionally, may contain at least one comonomer. Nonlimiting examples of an olefin-based polymer include an ethylene-based polymer and a propylene-based polymer.

[0030] A "polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term "homopolymer" (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure). A "copolymer" is a polymer having two polymer units that are different from each other. The term "different" in reference to polymer units indicates that the polymer units differ from each other by at least one atom or are different isomerically. As used herein a "polymerization process" is a process that is utilized to make a polymer. For instance, the polymerization process can be a gas-phase or slurry-phase polymerization process. In someembodiments, the polymerization process consists of a gas-phase polymerization process. In some embodiments the polymerization process consists of a slurry-phase polymerization process. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and / or within the polymer. It also embraces all forms of copolymer, e.g., random, block, etc. The terms "ethylene / a-olefin polymer" and "propylene / a-olefin polymer" are indicative of copolymer as described above prepared from polymerizing ethylene or propylene respectively and one or more additional, polymerizable a-olefin monomer. It is noted that although a polymer is often referred to as being "made of" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, or the like, in this context the term "monomer" is understood to be referring to the polymerized remnant of the specified monomer and not to the unpolymerized species. In general, polymers herein are referred to as being based on "units" that are the polymerized form of a corresponding monomer.

[0031] A "precatalyst" refers to a transition metal compound that has olefin polymerization catalytic activity when combined with an activator.

[0032] The term "spray drying" refers to the method of combining the activator, a support material, an inert hydrocarbon solvent and optionally one or more precatalysts to make a mixture, and removing the inert hydrocarbon solvent via spray drying from the mixture so as to yield a spray dried compound.DETAILED DESCRIPTION

[0033] The present disclosure provides a catalyst system. In an embodiment, the catalyst system includes a precatalyst. The precatalyst includes a phenoxy imine precatalyst of Formula 1 shown below. In Formula 1, each of R1is independently selected from a C5 to C20 alkyl group. Each of X is independently selected from a halogen atom.(Formula 1).

[0034] The catalyst system includes the precatalyst. The precatalyst is a phenoxy imine precatalyst having the structure of Formula 1. Each R1group can be the same or different. Each R1group is selected from a C5 to C20 alkyl group, or a Ce to Cis alkyl group, or a C7 to C15 alkyl group, or a Cs to C12 alkyl group. Each X group can be the same or different. Each X group is a halogen atom selected from fluorine, chlorine (Cl), iodine, and bromine.

[0035] In an embodiment, the phenoxy imine precatalyst having the structure of Formula 1 includes R1groups that are the same and X groups that are the same. Each R1group is a C& to Cis alkyl group and each X group is a chlorine atom.

[0036] In an embodiment, the phenoxy imine precatalyst includes R1groups that are the same, each R1group being a linear Cs alkyl group and X groups that are the same, each X group is a chlorine atom. The phenoxy imine precatalyst has the structure of Formula 2 below.(Formula 2).

[0037] In an embodiment, the phenoxy imine precatalyst includes R1groups that are the same, each R1group being a branched Cs alkyl group and X groups that are the same, each X group is a chlorine atom. Each R1group is a 1,1,3,3-tetramethylbutyl group. The phenoxy imine precatalyst has the structure of Formula 3 below.(Formula 3).

[0038] In an embodiment, the catalyst system also includes an activator. As used herein, "activator" refers to any compound or combination of compounds, supported, or unsupported, which can activate a complex or a precatalyst, such as by creating a cationic species of the precatalyst. For example, the activator can include the abstraction of at least one leaving group, e.g., from the zirconium metal center of the complex / catalyst component, e.g., the metalcomplex of Formula 1. As used herein, "leaving group" refers to one or more chemical moieties bound to a metal atom and that can be abstracted by an activator, thus producing a species active towards olefin polymerization.

[0039] The activator can include a Lewis acid or a non-coordinating ionic activator or ionizing activator, or any other compound including Lewis bases, aluminum alkyls, and / or conventional- type co-catalysts.

[0040] In an embodiment, the activator is an aluminoxane. An "aluminoxane" is an oligomeric aluminum compound having -AI(R)-O- subunits, where R is an alkyl group. Aluminoxanes can be produced by the hydrolysis of the respective trialkylaluminum compound. Modified methyl aluminoxane ("MMAO") can be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum, such as triisobutylaluminum. There are a variety of known methods for preparing aluminoxane and modified aluminoxanes. The aluminoxane can include a modified methyl aluminoxane ("MMAO") type 3A (commercially available from Nouryon under the trade name Modified Methylaluminoxane type 3A, discussed in U.S. Patent No. 5,041,584). A source of methyl aluminoxane ("MAO") can be a solution having from about 1 wt. % to about a 50 wt. % MAO, for example. Commercially available MAO solutions can include the 10 wt. % and 30 wt. % MAO solutions available from W. R. Grace, of Baton Rouge, LA.

[0041] In addition to methylaluminoxane ("MAO") and modified methylaluminoxane ("MMAO"), illustrative activators can include, but are not limited to, aluminoxane or modified aluminoxane, and / or ionizing compounds, neutral or ionic, such as dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(3,5-(CF3hphenyl)borate, triphenylcarbenium tetrakis(3,5- (CFshphenylJborate, dimethylanilinium tetrakis(perfluoronapthyl)borate, triphenylcarbenium tetrakis(perfluoronapthyl)borate, dimethylanilinium tetrakis(pentafluorophenyl)aluminate, triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, dimethylanilinium tetrakis(perfluoronapthyl)aluminate, triphenylcarbenium tetrakis(perfluoronapthyl)aluminate, a tris(perfluorophenyl)boron, a tris(perfluoronaphthyl)boron, tris(perfluorophenyl)aluminum, a tris(perfluoronaphthyl)aluminum or any combinations thereof.

[0042] One or more organo-aluminiim compounds, such as one or more alkylaluminum compound, can be used in conjunction with the aluminoxanes. Examples of alkylaluminum compounds include, but are not limited to, diethylaluminum ethoxide, diethylaluminum chloride, diisobutylaluminum hydride, and combinations thereof. Examples of other alkylaluminum compounds, e.g., trialkylaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum ("TEAL"), triisobutylaluminum ("TiBAI"), tri-n- hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and combinations thereof.

[0043] In an embodiment, the activator is provided on a support. The support may be a porous support material, for example, talc, an inorganic oxide, or an inorganic chloride. Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0044] Support materials include inorganic oxides that include Group 2, 3, 4, 5, 13 or 14 metal oxides. Nonlimiting examples of suitable supports include silica, fumed silica, alumina, silica- alumina, and mixtures thereof. Some other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays) and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica-titania and the like. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymeric beads.

[0045] A nonlimiting example of a support is fumed silica available under the trade name Cabosil ™ TS- 610, or other TS- orTG-series supports, available from Cabot Corporation. Fumed silica is typically a hydrophobic silica with low surface area and a submicron particle size that has been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

[0046] In an embodiment, the support material has a surface area in the range from 10 m2 / g to 700 m2 / g, a pore volume in the range from 0.1 g / cm3to 4.0 g / cm3and an average particle size in the range from 0.05 to 500 ppm. In a further embodiment, the support material has asurface area from 50 to 500 m2 / g, a pore volume from 0.5 to 3.5 g / cm3and an average particle size of from 0.05 microns to 50 microns. In yet a further embodiment, the support material has a surface area range from 50 to 300 m2 / g, a pore volume from 0.8 to 3.0 g / cm3and an average particle size is from 0.1 microns to 10 microns. The support material typically has pore size in the range of from 10 angstroms (A) to 1000A, or from 50 to 500A, or from 75 to 350A.

[0047] The support material may be an uncalcined material or a calcined material prior to being contacted with the activator. The solid support material may be a hydrophobic fumed silica (e.g., a fumed silica treated with dimethyldichlorosilane). The activator spray-dried to the support may be in the form of a powdery, free-flowing particulate solid.

[0048] In an embodiment, the activator is methylaluminoxane spray-dried to a hydrophobic fumed silica support.

[0049] In an embodiment, the catalyst system includes the phenoxy imine olefin polymerization precatalyst (Formula 2 or 3) and also includes at least one methylaluminoxane (MAO) activator spray-dried on a fumed silica support. In a further embodiment, the MAO is present at a ratio of 110 Al: Zr.

[0050] In an embodiment, the phenoxy imine precatalyst is dissolved in, or otherwise suspended in a hydrocarbon solvent (such as hexane for example). The phenoxy imine precatalyst is present from 0.01 wt% to 5 wt%, or from 0.04 wt% to 2 wt%, or from 0.44 wt% to 1.5 wt%, or 1.0 wt%, wherein weight percent is based on the total weight of the phenoxy imine precatalyst and solvent.

[0051] In an embodiment, the phenoxy imine precatalyst and the activator are dissolved in, or otherwise suspended in, a hydrocarbon solvent (such as hexane for example). The phenoxy imine precatalyst is present from 0.01 wt% to 5 wt%, or from 0.04 wt% to 2 wt%, or from 0.44 wt% to 1.5 wt%, or 1.0 wt%, wherein weight percent is based on the total weight of the phenoxy imine precatalyst, activator, and solvent. In a further embodiment, the activator is MAO and / or MMAO, such as spray-dried MAO on a fused silica support (or as spray-dried MMAO on a fused silica support).

[0052] In an embodiment, the phenoxy imine precatalyst exhibits no structural change when aged in anhydrous hexane for four weeks in an inert atmosphere at 25°C as measured by1HNMR. In a further embodiment, the phenoxy imine precatalyst exhibits no structural change when aged in anhydrous hexane for at least four weeks (28 days), or at least 10 weeks, or at least 12 months (1 year) in an inert atmosphere at 25°C as measured by1H NMR.

[0053] In an embodiment, the catalyst system includes the phenoxy imine precatalyst and the activator and the catalyst system also includes another catalyst (interchangeably referred to as "other catalyst"). The other catalyst is selected from bis (2-pentamethylphenylamido)ethyl)- amine zirconium dibenzyl) (Formula III), methylcyclopentadienyl)(l,3-dimethyl-4, 5,6,7- tetrahydroindenyl)zirconium dimethyl (Formula IV), ( / 75-cyclopentadienyl)( / 75-l,5- dimethylindenyl)zirconium dimethyl (Formula V), bis(n-butylcylcopentadienyl)zirconium dimethyl (Formula VI), and combinations thereof.

[0054] In an embodiment, the catalyst system includes the activator that is methylaluminoxane (MAO) (or MMAO) spray dried with a support material that is hydrophobic fumed silica. As disposed on the support material is the phenoxy imine precatalyst having the structure of Formula 1, and / or the other catalyst, selected from bis (2-pentamethylphenylamido)ethyl)- amine zirconium dibenzyl) (Formula III), methylcyclopentadienyl)(l,3-dimethyl-4, 5,6,7- tetrahydroindenyl)zirconium dimethyl (Formula IV), ( / 75-cyclopentadienyl)( / 75-l,5- dimethylindenyl)zirconium dimethyl (Formula V), bis(n-butylcylcopentadienyl)zirconium dimethyl (Formula VI), and combinations thereof. The term "disposed," "disposed on," and like terms refers to the physical contact between the support material (D) and the other components (A), and / or (B), and / or (C); the term "disposed on" including, but not limited to, deposited on, in contact with, vaporized with, bonded to, incorporated within, adsorbed on, and absorbed in.Process

[0055] The present disclosure provides a process. In an embodiment, the process includes polymerizing ethylene with one or more a-olefins, under polymerization conditions, with a catalyst system composed of a precatalyst and an activator. The precatalyst is a phenoxy imine precatalyst having the structure of Formula 1. The catalyst system also includes at least one spray-dried methyl aluminoxane activator. The process includes forming an ethylene / a-olefin copolymer.

[0056] The term "polymerization conditions," as used herein refers to a combination of polymerization condition parameters that may affect a polymerization reaction in a fluidized bed, gas-phase polymerization reactor ("FB-GPP reactor") reactor or a composition or property of a polymer composition product made thereby. The polymerization condition parameters may include reactor design and size, catalyst composition and amount; reactant composition and amount; molar ratio of different reactants; presence or absence of feed gases such as H2 and / or O2, molar ratio of feed gases versus reactants, absence or concentration of interfering materials (e.g., H2O), absence or presence of an induced condensing agent (ICA), average polymer residence time in the reactor, partial pressures of constituents, feed rates of monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, time periods for transitioning between steps. Parameters other than those being described or changed by the process may be kept constant.

[0057] The present polymerization conditions utilize a gas-phase polymerization (GPP) reactor, such as a stirred-bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gasphase polymerization reactor (FB-GPP reactor), to make the polymer composition. For example, the FB-GPP reactor / method may be as described in US 3,709,853; US 4,003,712; US 4,01 1 ,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541 ,270; EP-A-0 802 202; and Belgian Patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and processes either mechanically agitate or fluidize by continuous flow of gaseous monomer and diluent the polymerization medium inside the reactor, respectively. Other useful reactors / processes contemplated include series or multistage polymerization processes such as described in US 5,627,242; US 5,665,818; US 5,677,375; EP-A-0794 200; EP-B1 -0 649 992; EP-A-0802 202; and EP-B-634421.

[0058] In operating the present polymerization conditions the following polymerization condition parameters can be adjusted and / or controlled in a GPP, SB-GPP, or FB-GPP. Individual flow rates of ethylene ("C2"), hydrogen ("H2") and a-olefin (such as 1 -hexene ("Ce")) are controlled to maintain a fixed comonomer to ethylene monomer gas molar ratio (C6 / C2) equal to a described value (e.g., 0.002-0.04), a constant hydrogen to ethylene gas molar ratio ("H2 / C2") equal to a described value (e.g., 0 - 0.1), and a constant ethylene ("C2") partialpressure equal to a described value (e.g., 220-240 psi). Concentrations of gases are measured by an in-line gas chromatograph to maintain the composition in the recycle gas stream. A reacting bed of growing polymer particles is maintained in a fluidized state by continuously flowing a make-up feed and recycle gas through the reaction zone. The FB-GPP reactor is operated at a total pressure of 100 to 600 pounds per square inch-gauge (psig)) and at a described first reactor bed temperature ("RBT"). The fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of production of particulate form of the polymer composition. The product polymer composition is removed semi-continuously via a series of valves into a fixed volume chamber, wherein the removed polymer composition is purged to remove entrained hydrocarbons and treated with a stream of humidified nitrogen (N2) gas to deactivate any trace quantities of residual catalyst.

[0059] In some embodiments the FB-GPP reactor is a commercial scale reactor such as a UNIPOL™ reactor or UNIPOL™ II reactor, which are available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA.

[0060] The polymerization conditions may further include one or more additives such as a chain transfer agent or a promoter. The chain transfer agent may be an alkyl metal such as diethyl zinc. Promoters are known such as in US 4,988,783 and may include chloroform, CFCI3, trichloroethane, and difluorotetrachloroethane. Prior to reactor start up, a scavenging agent may be used to react with moisture and during reactor transitions a scavenging agent may be used to react with excess activator. Scavenging agents may be a trialkylaluminum. Gas phase polymerizations may be operated free of (not deliberately added) scavenging agents. The polymerization conditions for gas phase polymerization reactor / method may further include an amount (e.g., 0.5 to 200 ppm based on all feeds into reactor) of a static control agent and / or a continuity additive such as aluminum stearate or polyethyleneimine. The static control agent may be added to the FB- GPP reactor to inhibit formation or buildup of static charge therein.

[0061] In an embodiment, the process includes contacting the activator with the precatalyst. Each contacting step between activator and precatalyst independently may be done either (a) in a separate vessel outside the GPP reactor (e.g., outside the FB-GPP reactor), (b) in a feed line to the GPP reactor, and / or (c) inside the GPP reactor (in situ). In option (a) the catalyst system,once the precatalyst is activated, may be fed into the GPP reactor as a slurry in mineral oil and optionally a non-polar, aprotic (hydrocarbon) solvent (i.e., a pre-mix of precatalyst and activator in hydrocarbon solvent). In option (c) the precatalyst may be fed into the reactor prior to activation via a first feed line, and the activator may be fed into the reactor via a second feed line. The activator(s) may be fed into the reactor in "wet mode" in the form of a solution thereof in an inert liquid such as mineral oil or toluene, in slurry mode as a suspension, or in dry mode as a powder. Each contacting step may be done in separate vessels, feed lines, or reactors at the same or different times, or in the same vessel, feed line, or reactor at different times, to separately give the catalyst system. Alternatively, the contacting steps may be done in the same vessel, feed line, or reactor at the same time to give a mixture of the precatalyst and activator in situ.

[0062] The process includes polymerizing, or otherwise contacting, ethylene with one or more olefins, under polymerization conditions, with the catalyst system. As used herein, an "olefin," refers to a linear, branched, or cyclic compound including carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer is referred to as comprising, e.g., being made from, an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 75 wt% to 85 wt%, it is understood that the polymer unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present at 75 wt% to 85 wt%, based upon the total weight of the polymer. A higher a-olefin refers to an a-olefin having 3 or more carbon atoms.

[0063] In an embodiment, the one or more olefins include one or more a-olefins. Nonlimiting examples of suitable a-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l- pentene, 1-octene, 3,5,5-trimethyl-l-hexene, and any combination thereof.

[0064] In an embodiment, polymerization of ethylene and a C4-C8 a-olefin comonomer is performed in an autoclave polymerization reaction equipped with a mechanical agitator. SMAO (silica supported methylaluminoxane) is added as a scavenger under nitrogen pressure and the reactor is subsequently charged with hydrogen. The reactor temperature is from 75°C to 110°C and the reactor pressure is from 200 psi to 250 psi. Once the pressurized reactorreaches a steady state, the catalyst system comprising of precatalyst of Formula (1) and an activator is charged to the reactor to start the polymerization. Gas molar ratios are maintained throughout the polymerization with a continuous sample stream for molar concentration measurement by a mass spectrometer. Reaction time (or residence time) is from 0.5 hours to 4.0 hours, or from 1.0 hours to 3.0 hours. Upon completion of polymerization, the reactor is then cooled to ambient temperature vented and opened.

[0065] The process includes forming an ethylene / a-olefin copolymer (or ethylene / a-olefin terpolymer). Examples of polyolefins include ethylene-based polymers, having at least 50 mol ethylene, including ethylene-l-butene, ethylene-l-hexene, and ethylene-l-octene copolymers, among others.

[0066] In an embodiment, other olefins that may be utilized include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins, for example. Examples of the monomers may include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene. In a number of embodiments, a copolymer of ethylene can be produced, where with ethylene, a comonomer having at least one a-olefin having from 4 to 15 carbon atoms, or from 4 to 12 carbon atoms, or from 4 to 8 carbon atoms, is polymerized, e.g., in a gas-phase polymerization process.

[0067] In an embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers, optionally one of which may be a diene, to make a copolymer. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0068] The ethylene / a-olefin copolymer (or terpolymer) can include from 50 to 95 wt % of units derived from ethylene and 50-5 wt% of one or more olefins based on a total weight of the polymer. All individual values and subranges from 50 to 95 wt % are included; for example, the polymer can include from a lower limit of 50, 60, or 70 wt % of units derived from ethylene to an upper limit of 95, 90, or 85 wt % of units derived from ethylene based on the total weight ofthe polymer. The polymer can include from 5 to 50 wt % of units derived from comonomer based on the total weight of the polymer.

[0069] In an embodiment, the catalyst system includes the phenoxy imine precatalyst and the activator and the catalyst system also includes another catalyst (interchangeably referred to as "other catalyst"). The other catalyst is selected from bis (2-pentamethylphenylamido)ethyl)- amine zirconium dibenzyl) (Formula III), methylcyclopentadienyl)(l,3-dimethyl-4, 5,6,7- tetrahydroindenyl)zirconium dimethyl (Formula IV), ( / 75-cyclopentadienyl)( / 75-l,5- dimethylindenyl)zirconium dimethyl (Formula V), bis(n-butylcylcopentadienyl)zirconium dimethyl (Formula VI), and combinations thereof. With the inclusion of the other catalyst, the process includes forming a bimodal ethylene / a-olefin copolymer, or forming a trimodal ethylene / a-olefin copolymer.

[0070] In an embodiment, the process includes contacting the spray-dried supported activated other catalyst with the phenoxy imine precatalyst which is dissolved in hydrocarbon solvent.

[0071] In an embodiment, the polymerization conditions include a gas-phase polymerization reactor, and the process includes contacting the activated precatalyst of Formula (1) with the ethylene and C4-C8 a-olefin comonomer ( / .e., hexene) under polymerization conditions, and controlling, providing, or otherwise adjusting one, some, or all of the following variables:(i) a reaction temperature from 75°C to 110°C, or from 75°C to 105°C, or from 80°C to 100°C, and / or(ii) a molar ratio of the hydrogen gas to the ethylene of 0, or from greater than 0 to 0.10, or from 0.0005 to 0.010, or from 0.001 to 0.007 and / or,(iii) a molar ratio of the hexene to the ethylene of 0, or from greater than O to 0.04, or from 0.0030 to 0.020, or from 0.004 to 0.016, and / or(iv) a reactor residence time from 0.5 hours to 4.0 hours, or from 1.0 hours to 4.0 hours, or from 1.0 to 3.0 hours, or from 1.0 to 2 hours, and the process includes forming an ethylene / hexene copolymer having one, some or all of the following properties:(i) a melting temperature (Tm) from 110°C to 138°C, or from 125°C to 138°C, or from 128°C to 137°C, or from 130°C to 136°C; and / or(ii) a density from 0.900 g / cc to 0.970 g / cc, or from 0.910 g / cc to 0.965 g / cc, or from 0.920 g / cc to 0.930 g / cc, and / or(iii) a melt index (I?) of 0 g / lOmin, or from 1 g / lOmin to 1000 g / lOmin, or from 2g / 10min to 800g / 10min; and / or(iv) a high load melt index (121) from 2 g / 10 min to 1500 g / 10 min, and / or(v) a molecular mass dispersity (Mw / Mn) from 1.0 to 35.0, or from 2.0 to 35.0, or from 2.0 to 15.0, or from 2.0 to 14.0; and / or(vi) a weight-average molecular weight (Mw) from 15,000 g / mol to 500,000 g / mol, or from 15,000 g / mol to 130,000 g / mol, or from 18,000 g / mol to 127,000 g / mol, or from 100,000 g / mol to 500,000 g / mol; and / or(vii) a number-average molecular weight (Mn) from 5,000 g / mol to 180,000 g / mol, or from 5,000 g / mol to 20,000 g / mol, or from 6,000 g / mol to 16,000 g / mol or from 7,395 g / mol to 14,077 g / mol; and / or(vi) a z-average molecular weight (Mz) from 35,000 g / mol to 6,200,000 g / mol, or from 35,000 to 5,500,000 g / mol.

[0072] In the present phenoxy imine precatalyst, each R1group is located at the ortho- position relative to the phenol group on the benzene ring. The present phenoxy imine precatalyst also includes a C4 group located at the para- position of each benzene ring. Applicant discovered that the provision of R1as a C5 to C20 alkyl group (at the ortho- position) and C4 group at the para- position yields asymmetry in the phenoxy imine precatalyst molecule (hereafter interchangeably referred to as "substituent asymmetry"). This substituent asymmetry surprisingly improves, or otherwise increases, the solubility of the phenoxy imine precatalyst in alkane solvent (such as hexane, for example). Under polymerization conditions in a single gas phase polymerization reactor, the substituent asymmetry in the present phenoxy imine catalyst also contributes to (i) increasing the ethylene to comonomer selectivity, (ii) the ability to adjust the high molecular weight tail, (iii) the low hydrogen response of the present phenoxy imine catalyst, thereby producing ethylene / a-olefin copolymer (or ethylene / a-olefin terpolymer) with (iv) high vinyl content and (v) a substantial HMW component.

[0073] The ethylene / a-olefin copolymer (or ethylene / a-olefin terpolymer) can be utilized for a number of articles such as films, fibers, nonwoven and / or woven fabrics, extruded articles, and / or molded articles, among others.TEST METHODS

[0074] Differential Scanning Calorimetry (DSC). Melt temperature can be determined via Differential Scanning Calorimetry according to ASTM C 3418-08. For instance, using a scan rate of 10° C. / min on a sample of 10 mg and using the second heating cycle.

[0075] Gel permeation chromatography (GPC) Test Method: Weight-Average Molecular Weight Test Method: determine molecular weight (Mw), number-average molecular weight (Mn), average molecular weight (Mz), peak molecular weight (Mp), and Mw / Mn(PDI) are determined by using chromatograms obtained on a High Temperature Gel Permeation Chromatography instrument (HTGPC, Polymer Laboratories). The HTGPC is equipped with transfer lines, a differential refractive index detector (DRI), and three Polymer Laboratories PLgel 10pm Mixed-B columns, all contained in an oven maintained at 160° C. Method uses a solvent composed of BHT-treated TCB at nominal flow rate of 1.0 milliliter per minute (mL / min.) and a nominal injection volume of 300 microliters (4). Prepare the solvent by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent grade 1,2,4- trichlorobenzene (TCB), and filtering the resulting solution through a 0.1 micrometer (pm) Teflon filter to give the solvent. Degas the solvent with an inline degasser before it enters the HTGPC instrument. Calibrate the columns with a series of monodispersed polystyrene (PS) standards. Separately, prepare known concentrations of test polymer dissolved in solvent by heating known amounts thereof in known volumes of solvent at 160 °C. with continuous shaking for 2 hours to give solutions. (Measure all quantities gravimetrically.) Target solution concentrations, c, of test polymer of from 0.5 to 2.0 milligrams polymer per milliliter solution (mg / mL), with lower concentrations, c, being used for higher molecular weight polymers. Prior to running each sample, purge the DRI detector. Then increase flow rate in the apparatus to 1.0 mL / min / and allow the DRI detector to stabilize for 8 hours before injecting the first sample.Calculate Mwand Mnusing universal calibration relationships with the column calibrations.Calculate MW at each elution volume with following equation:where subscript "X" stands for the test sample, subscript "PS" stands for PS standards, aps=0.67, Kps=0.00017:, and axand Kxare obtained from published literature. For polyethylenes, ax / Kx= 0.695 / 0.000579. For polypropylenes ax / Kx= 0.705 / 0.0002288. At each point in the resulting chromatogram, calculate concentration, c, from a baseline-subtracted DRI signal IDRI, using the following equation: C= KoRilDRi / (dn / dc), wherein KDRI is a constant determined by calibrating the DRI, / denotes division and dn / dc is the refractive index increment for the polymer. For polyethylene, dn / dc = 0.109. Calculate mass recovery of polymer from the ratio of the integrated area of the chromatogram of concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. Report all molecular weights in grams per mole (g / mol) unless otherwise noted. Further details regarding methods of determining Mw, Mn, MWD are described in US 2006 / 0173123 page 24- 25, paragraphs

[0334] to

[0341] , Plot of dW / dLog(MVV) on the y-axis versus Log(MW) on the x- axis to give a GPC chromatogram, wherein Log(MW) and dW / dLog(MVV) are as defined above.

[0076] Comonomer content (i.e., 1-hexene) incorporated in the polymers (weight %) is determined by rapid FT-IR spectroscopy on the dissolved polymer in a GPC measurement. Comonomer content may be determined with respect to polymer molecular weight by use of an infrared detector such as an IR5 detector in a gel permeation chromatography measurement, as described in Analytical Chemistry 2014, 86(17), 8649-8656. "Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors" by Dean Lee, Colin Li Pi Shan, David M. Meunier, John W. Lyons, Rongjuan Cong, and A. Willem deGroot. Analytical Chemistry 201486 (17), 8649-8656

[0077] Melt Indices. Melt index ("l2") Test Method: for ethylene-based (co)polymer is measured according to ASTM D1238, using condition B atl90° C. / 2.16 kg. ("Is") Test Method:for ethylene-based (co)polymer is measured according to ASTM D1238, using condition Bat 190° C. / 5.16 kg. High Load Melt Index ("I21") is measured according to ASTM D1238, using condition Bat 190° C. / 21 .6 kilograms (kg). Report results in units of grams eluted per 10 minutes (g / 10 min.).

[0078] XH nuclear magnetic resonance (1H NMR) Test Method: Long term storage stability of the phenoxy imine precatalysts were evaluated by1H NMR.1H NMR spectra were recorded on a Bruker AV400 NMR spectrometer (FT, 400 MHz2H) in deuterated benzene at ambient probe temperatures (25 °C). Chemical shifts are reported in parts per million (ppm) down field relative to tetramethylsilane (TMS) using residual protons in deuterated solvent references. TheTH NMR chemical shift data measured in deuterated benzene is referenced to 7.16 ppm. Samples for long term storage stability studies were prepared by dissolving the desired phenoxy imine precatalyst to the target concentration in hexane. These phenoxy imine solutions were stored at ambient temperature in the glove box or in the glove box freezer at -34 °C. An aliquot of the precatalyst solution in hexane was taken out periodically and the hexane solvent of the aliquot was removed under vacuum, dissolved in deuterated benzene and analyzed byTNMR. The decomposition in the chemical structure was characterized by disappearance of the signals assigned to the structure of the phenoxy imine precatalyst when it was first prepared, appearance of new signals not assigned to the structure of phenoxy imine precatalyst and changes in the peak integrals of signals assigned to the phenoxy imine precatalyst.XH NMR characterization was conducted periodically, in intervals for example of weeks months, up to one year.

[0079] Some embodiments of the present disclosure will now be described in detail in the following Examples.EXAMPLES

[0080] Table 1A below provides precatalysts, used to prepare the Comparative Samples (CS) and the Inventive Examples (IE).

[0081] Table 1A- Precatalysts

[0082] Table IB - Activator

[0083] Table 1C - Other catalysts1. Synthesis of the phenoxy imine precatalyst of Formula 2 and Formula 3

[0084] The synthetic schemes for the synthesis of Formula 2 is provided in FIG. 1. The synthetic schemes for the synthesis of Formula 3 is provided in FIG. 2.2. Preparation of Spray Dried Non-metallocene catalyst of Formula III (bis (2- pentamethylphenylamido)ethyl)-amine zirconium dibenzyl):

[0085] In a nitrogen-purged glove box, an oven-dried glass bottle is charged with 1.33 g of fumed silica (CAB-O-SIL® TS-610 Fumed Silica) and then slurried in 35 g of toluene until well dispersed. Then 11.0 g of a 10 wt.% solution of MAO in toluene and 0.078 g of Non-metallocene precatalyst of Formula III (bis (2-pentamethylphenylamido)ethyl)-amine zirconium dibenzyl) were added, after which the mixture was allowed to stir for 60 minutes. The mixture was spray- dried using a Buchi Mini Spray Dryer B-290 with the following parameters to yield the dried sample of CS3, CS4: Set Temperature of 140 °C, an outlet temperature of 75 °C (min.), aspirator setting of 60, and a pump speed of 130 rpm.

[0086] A spray dried activator system (SDMAO) was prepared as described above by excluding the addition of the non-metallocene precatalyst component.3. Polymerization

[0087] Polymerizations of IE1-IE26 and CS3-CS4 were conducted in the gas-phase in a 2L semi-batch autoclave polymerization reactor equipped with a mechanical agitator as follows. The reactor was first dried for 1 hour, charged with 200 g of sodium chloride (NaCI) and dried by heating at 100 °C under nitrogen for 1 hour. After drying, 5 grams of silica supported methylaluminoxane (SMAO) was introduced as a scavenger under nitrogen pressure. After adding the SMAO, the reactor was sealed, and components were stirred. The reactor was then pressurized with hydrogen. The reactor was then pressurized with hexene (at a ratio of 0.004 Ce / C2 or a ratio of 0.016 C5 / C2) simultaneously with ethylene (total pressure of 230 psi). Once pressurized, the reactor was maintained at a constant C2 / H2 and C6 / C2ratio as specified in Table 2. Once the system reached a steady state, the type and amount of respective activated catalyst as identified by Tables 1-2 for each of Inventive Example was charged into the reactor at a catalyst injection temperature as specified inTable 2 to start polymerization. The reactor was brought to the reactor temperature as specified in Table 2 and maintained at this temperature throughout the specified residence time. At the end of the run, the reactor was cooled down, vented, and opened. The resulting product mixture was removed, washed with water and isopropanol, then dried, yielding ethylene / hexene copolymer.

[0088] The results of polymerization activity (grams polymer / gram catalyst-hour) for I El- 15 are shown in Table 2. In Table 2, "Cat 2" indicates the precatalyst of Formula 2 and "Cat 3" indicates the precatalyst of Formula 3. Molecular weight distribution for resultant resins are also shown in Table 2. The results of polymerization activity (grams polymer / gram catalyst- hour) for IE20-IE26 and CS3-CS4 are shown in Table 3. In Table 3, "Cat 2" indicates the precatalyst of Formula 2 and "Cat III" indicates the precatalyst of Formula III. Molecular weight distributions for resultant resins are also shown in Table 3.

[0089] Each precatalyst in Table 2 is premixed with the spray dried methylaluminoxane (SDMAO) activator to promote contact with the activator prior to injection into the reactor as follows. For I El-4 and IE10-11, 0.017 g of SDMAO was suspended in 3 mL of hexane. 0.111 mL of the precatalyst of Formula 2 as a 1.0 wt% solution in hexane was added followed by 3 mL of hexane and allowed to mix for the desired length of time as specified in Table 2. For IE5-9 and IE12-15, 0.016 g of SDMAO was suspended in 3 mL of hexane. 0.28 mL of the precatalyst of Formula 3 as a 0.44 wt% solution in hexane was added, followed by 3 mL of hexane and allowed to mix for the desired length of time as specified in Table 2.

[0090] For IE20-IE21 and IE23-IE25, 0.005 g of spray dried catalyst of Formula III (bis (2- pentamethylphenylamido)ethyl)-amine zirconium dibenzyl) was suspended in 3 mL of methylcyclohexane. The desired quantity of the precatalyst of Formula 2 (as a 0.2 wt% solution in hexane) was added followed by 3 mL of methylcyclohexane and allowed to mix for 25 minutes before injection into the reactor. For CS3 and CS4, 0.005 g of spray dried catalyst of Formula III was suspended in 6 mL of methylcyclohexane and mixed for 25 minutes before injection into the reactor. For IE22 and IE26, 0.005 g of SDMAO was suspended in 3 mL of methylcyclohexane. 0.245 mLof the precatalyst of Formula 2 as a 0.2 wt% solution in methylcyclohexane was addedfollowed by 3 mL of methylcyclohexane and allowed to mix for 25 minutes before injection into the reactor.Table 2- Polymerization Parameters and Ethylene / Hexene Copolymer Properties*-precontact time between precatalyst and SDMAO (minutes)Table 3- Polymerization Parameters and Ethylene / Hexene Copolymer Properties for bimodal systems made with Phenoxy Imine catalyst of formula 2 and a second precatalyst of Formula IIIFor all samples in Table 3, the catalyst injection temperature was 80°C

[0091] As detailed in Table 2, the resultant ethylene / hexene copolymer resins of IE1-15 have one, some, or all, of the following properties:(i) a melting temperature (Tm) from 130.64°C to 135.7°C; and / or(ii) a melt index (I2) from 3.09g / 10min to 857g / 10min, and / or(iii) a molecular mass dispersity (Mw / Mn) from 2.28 to 12.09; and / or(iv) a weight-average molecular weight (Mw) from 18,362 to 126,085 g / mol; and / or(v) a number-average molecular weight (Mn) from 6,216 to 15,351 g / mol; and / or(vi) a z-average molecular weight (Mz) from 39,739 to 6,061,602 g / mol.

[0092] As detailed in Table 3, the resultant bimodal ethylene / hexene copolymer resins of IE20-21 and IE23-25 have one, some, or all, of the following properties:(i) a melting temperature (Tm) from 127.53 °C to 131.58 °C; and / or(ii) a melt index (I2) from no flow to 0.026 / lOrnin, and / or(iii) a molecular mass dispersity (Mw / Mn) from 10.54 to 11.65; and / or(iv) a weight-average molecular weight (Mw) from 270,820 g / mol to 111,239 g / mol; and / or(v) a number-average molecular weight (Mn) from 19,383 g / mol to 10,542 g / mol; and / or(vi) a z-average molecular weight (Mz) from 1,941,367 g / mol to 1,270,260 g / mol.4. Solubility

[0093] Comparative Sample 1 (CS1): a precatalyst including phenoxy imine precatalyst of Formula 4 unsupported in a hydrocarbon (hexane) solvent.

[0094] Inventive Example 16 (IE16): a precatalyst including phenoxy imine precatalyst of Formula 2 unsupported in a hydrocarbon (hexane) solvent.

[0095] Inventive Example 17 (IE17): a precatalyst including phenoxy imine precatalyst of Formula 3 unsupported in a hydrocarbon (hexane) solvent.

[0096] The solubility of the phenoxy imine precatalysts in a saturated hydrocarbon solvent (hexane) was evaluated as follows for I E17.] . In the glove box, in a 40 mL glass vial 0.108 g of the phenoxy imine precatalyst of Formula 4 was dissolved in a minimum amount of hexane (37 mL, 24.38 g, density = 0.659 g / mL) until all the powder of the phenoxy imine precatalyst samplehad completely dissolved. The sample was stirred vigorously until the solution was completely homogeneous. The wt% solubility of phenoxy imine precatalyst of Formula 4 in hexane was determined by using this formula, shown for representative IE 17 = (0.108 g IE11) / ((0.108 g I Ell) + (24.38 g hexanes)) x 100% = 0.44 wt%. CS1 and I E17 were conducted in a similar manner.

[0097] The results of the solubility testing (wt%) CS1, and IE16-17 are shown in Table 4 below.

[0098] Table 4 - Solubility

[0099] The solubility experiments demonstrated that the phenoxy imine precatalysts of IE16 and I E17 exhibit a solubility requirement of greater than 0.1 wt% in a saturated hydrocarbon solvent such as hexane, pentane, heptane or Isopar. The solubility of the phenoxy imine precatalyst enables it to be well suited for use as an inert solution contacting a catalyst produce a low molecular weight component in a bimodal polymer system.

[0100] The substitution on the para position of the phenol ring with a group that imparts higher solubility (long alkyl chain, i.e. n-octyl) such as in IE 16 and IE 17 may provide for a more long-term stable zirconium dichloride phenoxy imine precatalyst as compared to CS1, which has relatively poorer solubility in saturated hydrocarbon solvent, with a solubility of less than 0.1 wt% in hexane.5. Stability

[0101] The long-term storage stability of the phenoxy imine precatalyst Formula 5, and inventive precatalysts Formula 2 and Formula 3, was evaluated by1H NMR testing. Each precatalyst was dissolved in hexane to target the concentration as shown in Table 5 below.

[0102] Table 5

[0103] Then, each precatalyst / hexane solution (CS12, 1 E18, 1 E19) was stored at ambient temperature (25°C) in the glove box or in the glove box freezer at -34 °C, respectively according to the duration of time specified in Tables 6A-6C, below. An aliquot of the solution was taken out periodically, the hexane solvent was removed under vacuum and characterization was conducted by1H NMR. The decomposition in the chemical structure was characterized by disappearance of the peaks (and / or the appearance of new peaks) assigned to the structure of the corresponding phenoxy imine precatalyst, relative to when the solution was first prepared, i.e. Day 1.1H NMR characterization was conducted periodically, in week intervals as shown in Tables 6A-6C.

[0104] Table 6A corresponds to FIG. 3A(i) and FIG. 3A(ii) (CS12 Formula 5), Table 6B corresponds to FIG. 3 B(i) and FIG. 3 B(ii) (IE18 Formula 2), and Table 6C corresponds to FIG. 3C(i) and FIG. 3C(ii) (IE19 Formula 3). The long-term storage stability was determined by the least decomposition reached by the solution sample as characterized byNMR. Distinct hydrogens are labeled in each precatalyst structure, with hydrogens identified on the spectrum for each respective precatalyst sample.

[0105] Table 6A- CS12 (Precatalyst Formula 5), corresponds to FIG. 3A(i) and FIG. 3A(ii)

[0106] A "structural change," to the precatalyst, as used herein, is defined as (i) the formation, or appearance, of new peaks, or (ii) a change to the integral area under an existing peak as determined by2H NMR, when the precatalyst is aged in anhydrous hexane for 2 weeks, 4 weeks, 10 weeks, or 12 months, or 14 months at 25°C.

[0107] In Table 6A and FIGS 3A(i), 3 A(ii), (CS12 Formula 5) new peaks identified by the areas outlined with boxes and arrows are detected as CS12 decomposes over time. The new peaks identified by boxes and arrows in FIG. 3A(i i) provide evidence for structural changes and the decomposition that occurs with aging of the precatalyst of Formula 5. Further evidence of structural changes as CS12 (Formula 5) decomposes can be seen by the changing integrals in aging experiments 1 and 3. In aging experiment 1, the ratio of integrals for peaks G:A:C:D:E are 1:1:1:3:3. After aging the precatalyst solution for 4 weeks at room temperature (25°C), evidence of precatalyst degradation ( / .e., evidence of precatalyst structure change) can be observed as the ratio for the integrals for peaks G:A:C:D:E are now 1:1.6:3:4.5:3.

[0108] Table 6B - I E18 (Preatalyst Formula 2) corresponds to FIG. 3 B(i) and FIG. 3B(ii)

[0109] In Table 6B and FIG. 3 B(ii ) ( I E18, Formula 2) no structural changes occur over the same period of time or longer period of time when I E18 is exposed to the same conditions as is CS12. IE18 does not show any new peaks over the same period of time or longer when IE18 is exposed to the same conditions as is CS12. I E18 does not show any significant change in the ratio of the integrals for the same corresponding protons. In aging experiment 1, the ratio of integral peaks F: A:C:D:E are 1:1 :1:3:3. After aging the precatalyst solution (IE 18, Formula 2) for 12 days, 10 weeks, and 13 months at room temperature (25°C), no structural change (no precatalyst degradation) can be observed as the ratio for the integrals for peaks F :A:C:D :E are now 1.0:0.96:1.15:3.10:2.86.

[0110] Table 6C - IE19 (Precatalyst Formula 3) corresponds to FIG. 3C(i) and FIG. 3C(ii)

[0111] In Table 6C and FIG. 3C(ii) (IE19, Formula 3) no structural changes occur over the same or longer period of time when I E 19 is exposed to the same conditions as is CS12. I E19 does not show any new peaks over the same period of time or longer when I E19 is exposed to the same conditions as is CS12. I E19 does not show any significant change in the ratio of the integrals for the same corresponding protons. In aging experiment 1, the ratio of integral peaks K:B:C:D:E are 1:1:1:3:3. After aging the precatalyst solution (IE 19, Formula 3) for 2 weeks, 4 weeks, and 14 months at room temperature (25°C), no structural change (no precatalyst degradation) can be observed as the ratio for the integrals for peaks K:B:C:D:E are now 1.0:1.01:1.11:3.38:3.19.

[0112] It is specifically intended that the present disclosure is not limited to the embodiments and illustrations contained herein but include modified forms of those embodiments including portions of the embodiments and combination of elements of different embodiments as come within the scope of the following claims.

Claims

CLAIMS1. A catalyst system, comprising: a precatalyst comprising a phenoxy imine precatalyst having a structure of Formula 1:(Formula 1) whereinR1each is independently a C5 to C20 alkyl group, and X each is independently a halogen atom.

2. The catalyst system of claim 1, wherein each of X is independently a chlorine atom.

3. The catalyst system of any of claims 1-2, wherein each of R1is independently a Cs alkyl group.

4. The catalyst system of claims 1-3 wherein each of R1is independently a linear Cs alkyl group and the phenoxy imine precatalyst has a structure of Formula 2Formula 2.

5. The catalyst system of claims 1-3, wherein each of R1is independently a 1,1, 3, 3- tetramethylbutyl group and the phenoxy imine precatalyst has a structure of Formula 3Formula 3.

6. The catalyst system of any of claims 1-5, wherein the catalyst system further comprises an activator.

7. The catalyst system of claim 6 wherein the activator is methylaluminoxane.

8. The catalyst system of any of claims 1-7 wherein the phenoxy imine precatalyst exhibits no structural change when aged in anhydrous hexane for four weeks in an inert atmosphere at 25°C as measured by1H NMR.

9. The catalyst system of any of claims 1-8 wherein the catalyst system comprises another catalyst selected from the group consisting of bis (2-pentamethylphenylamido)ethyl)-amine zirconium dibenzyl) (Formula III), methylcyclopentadienyl)(l,3-dimethyl-4, 5,6,7- tetrahydroindenyl)zirconium dimethyl (Formula IV), ( / 5-cyclopentadienyl)( / 75-l,5- dimethylindenyl)zirconium dimethyl (Formula V), bis(n-butylcylcopentadienyl)zirconium dimethyl (Formula VI), and combinations thereof.

10. A process comprising: polymerizing ethylene with one or more a-olefins, under polymerization conditions, with a catalyst system comprising(A) a phenoxy imine precatalyst having a structure of Formula 1(Formula 1)whereinR1each is independently a C5 to C20 alkyl group, andX each is independently a halogen;(B) an activator; and forming an ethylene / a-olefin polymer.

11. The process of claim 10 wherein the activator is methylaluminoxane.

12. The process of any of claims 10-11 comprising contacting the phenoxy imine precatalyst with the activator.

13. The process of any of claims 10-12 wherein the catalyst system comprises another catalyst selected from the group consisting of bis (2-pentamethylphenylamido)ethyl)-amine zirconium dibenzyl) (Formula III), methylcyclopentadienyl)(l,3-dimethyl-4, 5,6,7- tetrahydroindenyl)zirconium dimethyl (Formula IV), ( / 75-cyclopentadienyl)( / 75-l,5- dimethylindenyl)zirconium dimethyl (Formula V), bis(n-butylcylcopentadienyl)zirconium dimethyl (Formula VI), and combinations thereof.

14. The process of any of claims 10-13 wherein the polymerization conditions comprise a polymerization condition parameter selected from the group consisting of(i) a reaction temperature from 75°C to 110°C,(ii) a molar ratio of hydrogen gas to the ethylene from 0 to 0.10,(iii) a molar ratio of the a-olefin to the ethylene from 0 to 0.04,(iv) a reactor residence time from 1.0 hours to 4.0 hours, and(v) combinations thereof.

15. The process of any of claims 10-14 wherein the a-olefin is selected from the group consisting of (i) 1-butene, (ii) 1-hexene (iii) 1-octene, and (iv) combinations thereof, and the process comprises forming an ethylene / a-olefin copolymer having a property selected from the group consisting of(i) a melting temperature (Tm) from 110°C to 138°C,(ii) a density from 0.900 g / cc to 0.970 g / cc,(iii) a melt index (12) from 0 g / 10 min to 1000 g / 10 min,(iv) a high load melt index (121) from 2 g / 10 min to 1500 g / 10 min,(v) a molecular mass dispersity (Mw / Mn) from 1.0 to 35.0,(vi) a weight-average molecular weight (Mw) from 15,000 g / mol to 500,000 g / mol,(vii) a number-average molecular weight (Mn) from 5,000 to 180,000,(viii) a z-average molecular weight (Mz) from 35,000 g / mol to 6,200,000 g / mol, and(ix) combinations thereof.